Heterogeneous Catalysts. Группа авторов

[15, 65–67]. Datye and coworkers showed that at 800 °C in oxidizing ambient, Pt can transfer to ceria and be trapped there to form a sinter‐resistant, atomically dispersed catalyst [68]. Li and coworkers reported the successful reversion of sintering effects and the conversion of noble metal NPs into thermally stable and highly active SAs (Pd, Pt, Au) above 900 °C in an inert atmosphere by using nitrogen‐doped carbon derived from a metal–organic framework [69]. Such a high‐temperature atomic migration method requires a supply of mobile atoms and a support that can bind the mobile species. This method is potentially applicable for synthesizing high‐performance thermally stable SACs and reactivating sintered noble metal nanocatalysts.

Figure 6.8 (A) HAADF‐STEM image of Ag₁/HMO. (B) Three‐dimensional projected image of the dash rectangle in (A). (C) The shrinking process of the supported Ag NPs heated by an electron beam. (D) Three‐dimensional and contour maps of in situ differential XRD patterns of Ag_NP/HMO. (E) Ag K‐edge χ(R) k³‐weighted FT EXAFS spectra of the samples.

      Source: Adapted from Chen et al. 2015 [66] and Chen et al. 2016 [15].

      (See online version for color figure).

6.4 Challenges and Perspective

      SACs, as a kind of frontier catalysts, have attracted widespread attention and been extensively studied in recent years. Various methods have been developed to synthesize SACs, as summarized above. Specially, chemical methods are the most commonly used. Chemical methods can be categorized into two general approaches, i.e. bottom‐up and top‐down strategies. Although the top‐down strategy has provided a possibility to construct thermally stable SACs, it is still challenging to find practical methods for synthesizing stable SACs with high metal loadings.

      Liu et al. proposed that, in principle, there are three kinds of stability of SACs: intrinsic thermodynamic stability, kinetic stability, and dynamic stability. They suggested that the stability of SACs may depend not only on the support but also on the reaction conditions that are difficult to ascertain and vary from one system to another [70]. Strong metal–metal bonds or coordination bonds with O, N, S, or other atoms on supports may be the key for the stability of SACs. However, it is still challenging to regulate and control such metal–support interaction directly and efficiently. So far, successful examples on SACs are still limited in number [17, 18, 50, 71–73]. This situation calls for more fundamental research on detailed mechanisms.

      For future research, it is desirable to develop novel, controllable, and facile synthesis methods for obtaining high‐loading SACs with excellent stability for use in practical conditions. More advanced in situ techniques and theoretical calculations should be used to understand the nature of metal–support interactions comprehensively. In addition, more examples on the high efficiencies of these SACs in various catalytic reactions should be actively sought.

References

      1 1 Fürstner, A. (2009). Chem. Soc. Rev. 38: 3208–3221.

      2 2 Heck, R.M. and Farrauto, R.J. (2001). Appl. Catal., A 221: 443–457.

      3 3 Barakat, T., Rooke, J.C., Genty, E. et al. (2013). Energy Environ. Sci. 6: 371–391.

      4 4 Zhu, C., Du, D., Eychmüller, A., and Lin, Y. (2015). Chem. Rev. 115: 8896–8943.

      5 5 Liu, X., Iocozzia, J., Wang, Y. et al. (2017). Energy Environ. Sci. 10: 402–434.

      6 6 Liang, S., Hao, C., and Shi, Y. (2015). ChemCatChem 7: 2559–2567.

      7 7 Taylor, H.S. (1925). Proc. R. Soc. London, Ser. A 108: 105–111.

      8 8 de Heer, W.A. (1993). Rev. Mod. Phys. 65: 611–676.

      9 9 Valden, M., Lai, X., and Goodman, D.W. (1998). Science 281: 1647–1650.

      10 10 Lopez‐Acevedo, O., Kacprzak, K.A., Akola, J., and Häkkinen, H. (2010). Nat. Chem. 2: 329–334.

      11 11 Dahl, S., Logadottir, A., Egeberg, R.C. et al. (1999). Phys. Rev. Lett. 83: 1814–1817.

      12 12 Nøskov, J.K., Bligaard, T., Hvolbæ, B. et al. (2008). Chem. Soc. Rev. 37: 2163–2171.

      13 13 Schekhar, M., Wang, J., Lee, W. et al. (2012). J. Am. Chem. Soc. 134: 4700–4708.

      14 14 Cargnello, M., Doan‐Nguyen, V.V.T., Gordon, T.R. et al. (2013). Science 341: 771–773.

      15 15 Chen, Y., Huang, Z., Zhou, M. et al. (2016). Chem. Commun. 52: 9996–9999.

      16 16 Qiao, B., Wang, A., Yang, X. et al. (2011). Nat. Chem. 3: 634–641.

      17 17 Yang, X., Wang, A., Qiao, B. et al. (2013). Acc. Chem. Res. 46: 1740–1748.

      18 18 Liu, J. (2017). ACS Catal. 7: 34–59.

      19 19 Thomas, J.M. (1988). Angew. Chem. Int. Ed. Engl. 27: 1673–1691.

      20 20 Mascheyer, T., Rey, F., Sankar, G., and Thomas, J.M. (1995). Nature 378: 159–162.

      21 21 Abbet, S., Sanchez, A., Heiz, U. et al. (2000). J. Am. Chem. Soc. 122: 3453–3457.

      22 22 Thomas, J.M., Raja, R., and Lewis, D.W. (2005). Angew. Chem. Int. Ed. 44: 6456–6482.

      23 23 Böhme, D.K. and Schwarz, H. (2005). Angew. Chem. Int. Ed. 44: 2336–2354.

      24 24 Xing, J., Chen, J., Li, Y. et al. (2014). Chem. Eur. J. 20: 2138–2144.

      25 25 Yan, H., Cheng, H., Yi, H. et al. (2015). J. Am. Chem. Soc. 137: 10484–10487.

      26 26 von Weber, A., Baxter, E.T., White, H.S., and Anderson, S.L. (2015). J. Phys. Chem. C 119: 11160–11170.

      27 27 Zambelli, T., Wintterlin, J., Trost, J., and Ertl, G. (1996). Science 273: 1688–1690.

      28 28 Campbell, C.T. (2012). Nat. Chem. 4: 597–598.

      29 29 Fujitani, T. and Nakamura, I. (2011). Angew. Chem. Int. Ed. 50: 10144–10147.

      30 30 Imbihl, R. and Ertl, G. (1995). Chem. Rev. 95: 697–733.

      31 31 Yang, M., Allard, L.F., and Flytzani‐Stephanopoulos, M. (2013). J. Am. Chem. Soc. 135: 3768–3771.

      32 32 Zhang, L., Wang, A., Wang, W. et al. (2015). ACS Catal. 5: 6563–6572.

      33 33 Zhang, H., Wei, J., Dong, J. et al. (2016). Angew. Chem. Int. Ed. 55: 14310–14314.

      34 34 Hu, P., Huang, Z., Amghouz, Z. et al. (2014). Angew. Chem. Int. Ed. 53: 3418–3421.

      35 35 Chen, Y., Gao, J., Huang, Z. et al. (2017). Environ. Sci. Technol. 51: 7084–7090.

      36 36 Wang, L., Li, H., Zhang, W. et al. (2017). Angew. Chem. Int. Ed. 56: 4712–4718.

      37 37 Zhang, R., Lee, T.H., Yu, B. et al. (2012). Phys. Chem. Chem. Phys. 14: 16552–16557.

      38 38 Moses‐DeBusk, M., Yoon, M., Allard, L. et al. (2013). J. Am. Chem. Soc. 135: 12634–12645.

      39 39 Liang, J., Lin, J., Yang, X. et al. (2014). J. Phys. Chem. C 118: 21945–21951.

      40 40 Ding, W., Gu, X., Su, H., and Li, W. (2014). J. Phys. Chem. C 118: 12216–12223.

      41 41 Deng, D., Chen, X., Yu, L. et al. (2015). Sci. Adv. 1: e1500462.

      42 42 Choi, C.H., Kim, M., Kwon, H.C. et al. (2016). Nat. Commun. 7: 10922.

      43 43 Hackett, S.F., Brydson, R.M., Gass, M.H. et al. (2007). Angew. Chem. Int. Ed. 46: 8593–8596.

      44 44